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• W1994394497 endingPage "7376" @default.
• W1994394497 startingPage "7366" @default.
• W1994394497 abstract "A series of triazenide complexes of the heavier alkaline earths, Ca, Sr and Ba, have been synthesized by either protonolysis or salt metathesis routes. Although complexes of the form [{Ar2N3}M{N(SiMe3)2}(THF)n] (M = Ca, n = 2; M = Sr, n = 3; Ar = 2,6-diisopropylphenyl) and [{Ar2N3}Ca(I)(THF)2]2 could be isolated and characterized by X-ray crystallography, solution studies revealed the propensity of these species to undergo Schlenk-like redistribution with the formation of [{Ar2N3}2M(THF)n] (M = Ca, n = 1; M = Sr, n = 2). The latter compounds have been synthesized independently. In the case of the large barium dication, attempts to synthesize the heaviest analogue of the series, [{Ar2N3}2Ba(THF)n], failed and led instead to the isolation of the potassium barate complex [K{Ar2N3}Ba{N(SiMe3)2}2(THF)4]. Single crystal X-ray diffraction studies demonstrated that, although in all the aforementioned cases the triazenide ligand binds to the electrophilic group 2 metal centers via symmetrical κ2-N,N-chelates, in the latter compound an unprecedented bridging mode is observed in which the triazenide ligand coordinates through both terminal and internal nitrogen centers. A series of density-functional theory computational experiments have been undertaken to assist in our understanding of this phenomenon. In further experiments, the calcium and strontium amide derivatives [{Ar2N3}M{N(SiMe3)2}(THF)n] (M = Ca, n = 2; M = Sr, n = 3) proved to be catalytically active for the intramolecular hydroamination of 1-amino-2,2-diphenylpent-4-ene to form 2-methyl-4,4-diphenylpyrrolidine, with the calcium species demonstrating a higher turnover number than the strontium analogue (2a, TOF = 500 h−1; 2b, TOF = 75 h−1). In these instances, because of ambiguities in the structural charcterization of the precatalyst in solution, such quantification holds little value and detailed catalytic studies have not been conducted." @default.
• W1994394497 created "2016-06-24" @default.
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• W1994394497 date "2008-07-12" @default.
• W1994394497 modified "2023-10-15" @default.
• W1994394497 title "Triazenide Complexes of the Heavier Alkaline Earths: Synthesis, Characterization, And Suitability for Hydroamination Catalysis" @default.
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• W1994394497 doi "https://doi.org/10.1021/ic800789x" @default.
• W1994394497 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/18620384" @default.
• W1994394497 hasPublicationYear "2008" @default.
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